Supported polymerisation catalyst

ABSTRACT

The invention relates to supported ligands and catalysts for use in the polymerization of olefinically unsaturated monomers such as vinylic monomers, comprising the use of a compound attached to support, the compound being capable of complexing with a transitional metal. Preferably the compound capable of complexing with a transition metal is a diimine such as a 1,4-diaza-1,3-butadiene, a 2-pyridinecarbaldehyde imine, an oxazolidone or a quinoline carbaldeyde. Preferably the catalysts are used in conjunction with an initiator comprising a homolytically cleavable bond with a halogen atom. The application also discloses processes for attaching ligands to supports, and processes for using the catalysts disclosed in the application.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates to immobilised supported polymerisationcatalysts for atom transfer polymerisation of olefinically unsaturatedmonomers in which molecular weight control is achieved by the presenceof certain transition metal, especially copper, complexes.

2. Description of Related Art

It is desirable to be able to produce high molecular weight polymerswith a low molecular weight distribution by catalysed additionpolymerisation, in particular of vinylic monomers. Hitherto this hasbeen achieved by polymerising via ionic processes typically in thepresence of organometallics such as alkyl lithiums which are sensitiveas regards reaction with water and other protic species. As such,monomers containing functional groups are not readily polymerised. Theuse of ionic systems also precludes the use of solvents which containprotic groups and/or impurities resulting in very stringent reactionconditions and reagent purity being employed.

More recently atom transfer polymerisation based on the combination of atransition metal halide and alkyl halide have been utilised. Forexample, Matyjasewski (Macromolecules (1995), vol. 28, pages 7901-7910and WO96/30421) has described the use of CuX (where X=Cl, Br) inconjunction with bipyridine and an alkyl halide to give polymers ofnarrow molecular weight distribution and controlled molecular weight.This system suffers from the disadvantage that the copper catalyst ispartially soluble in the system and thus a mixture of homogeneous andheterogeneous polymerisation ensues. The level of catalyst which isactive in solution is thus difficult to determine. The catalyst residueswhich are soluble in the reaction medium prove difficult to remove fromthe product. Percec (Macromolecules, (1995), vol. 28, page 1995) hasextended Matyjasewski's work by utilising arenesulphonyl chlorides toreplace alkyl chlorides, again this results in a mixture of homogeneousand heterogeneous polymerisation and catalyst residues are difficult toremove from the product. Sawamoto (Macromolecules, (1995), vol. 28, page1721 and Macromolecules, (1997), vol. 30, page 2244) has also utilised aruthenium based system for similar polymerisation of methacrylates. Thissystem requires activation of monomer by an aluminum alkyl in order toachieve the best results, itself sensitive to reaction with proticspecies which is an inherent disadvantage. These systems have beendescribed as proceeding via a free radical mechanism which suffers fromthe problem that the rate of termination is >0 due to normalradical-radical combination and disproportionation reactions.

The inventors have found that the use of diimines such as1,4-diaza-1,3-butadienes and 2-pyridinecarbaldehyde imines may be usedin place of bipyridines. These ligands offer the advantage ofhomogeneous polymerisation and thus the level of active catalyst can beaccurately controlled and only one polymerisation process ensues. Thisclass of ligand also enables the control of the relative stability ofthe transition metal valencies, for example, Cu(I) and Cu(II), byaltering ancillary substituents and thus gives control over the natureof the products through control over the appropriate chemicalequilibrium. Such a system is tolerant to trace impurities, trace levelsof O₂ and functional monomers, and may even be conducted in aqueousmedia. This system is the subject of copending patent application numberPCT/GB97/01587.

A further advantage of this system is that the presence of free-radicalinhibitors traditionally used to inhibit polymerisation of commercialmonomers in storage, such as 2,6-di-tert-butyl-4-methylphenol (topanol),increases the rate of reaction of the invention. This means that lengthypurification of commercial monomers to remove such radical inhibitors isnot required. Furthermore, this indicates that the system is not afree-radical process. This is contrary to Matajaszewski and Sawamoto whoshow free-radical based systems.

A difficulty identified by the inventors for the commercialisation ofthe radical polymerisation system of Matajazewski and Sawamoto, and thediimine-based system described above is that high levels of catalystsare required for acceptable rates of polymerisation. This means thatcatalyst is relatively expensive as it is not recycled/reused and itmust be removed by lengthy procedures to prevent contamination of thefinal product and to keep production costs down.

SUMMARY OF THE INVENTION

The inventors have therefore identified a process for attaching thecatalyst to supports which allows the catalyst to be easily recoveredand produces products with substantially less contamination thanpreviously described systems.

Such supported catalysts were expected by the inventors to clumptogether since each metal ion can coordinate with two-ligands, each ofwhich is attached to a support. This would reduce the effectiveness ofsuch supported systems. However, this has not been observed by theinventors. Furthermore, the metal ion is tightly bound to the ligandsand does not leach off into the surrounding solution or product,allowing it to be reused.

A first aspect of the invention provides a supported ligand for use incatalysts for polymerisation of olefinically unsaturated monomers,especially vinylic monomers, said ligand being one or more compoundsattached to a support.

Such a ligand has general formula:

S(D)_(n)  FORMULA 1

where:

S is the support,

D is a compound attached to the support, said compound being capable ofcomplexing with a transition metal, and

n is an integer of one or more.

Preferably, the support is inorganic, such as silica, especially silicagel. Alternatively the support may be organic, especially an organicpolymer, especially a cross-linked organic polymer, such aspoly(styrene-w-divinylbenzone). Preferably the support is in the form ofbeads. This latter form is particularly advantageous because it has ahigh surface area which allows the attachment of a large number ofcompounds, whilst presenting a large surface area to the medium to becatalysed.

The compound (D) may be adsorbed onto the support or covalently attachedto the support.

Preferably the compound is an organic compound comprising Schiff base,amine, hydroxyl, phosphine or diimine capable of complexing with atransition metal ion. Each Schiff base, amine, hydroxyl, phosphine ordiimine is preferably separated from the support by a branched orstraight alkyl chain, especially a chain containing 1 to 20 carbonatoms. The chain may comprise one or more aromatic groups as part of thealkyl chain.

One preferred ligand is the use of a support attached to two or morealkyl-amines, such as aminopropyl-, aminobutyl-, aminopentyl-,aminohexyl-, aminoheptyl- or aminooctyl-functionalised support. Theamine groups are capable of forming a complex with one or moretransition metal ions.

Especially preferred compounds are diimines.

Preferably one of the nitrogens of the diimine is not part of anaromatic ring.

Preferably the diimine is a 1,4-diaza-1,3-butadiene

where R₁, R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be varied independently and R₁,R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be H, straight chain, branched chain orcyclic saturated alkyl, hydroxyalkyl, carboxyalkyl, aryl (such as phenylor phenyl substituted where substitution is as described for R₄ to R₉),CH₂Ar (where Ar=aryl or substituted aryl) or a halogen. Preferably R₁,R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be a C₁ to C₂₀ alkyl, hydroxyalkyl orcarboxyalkyl, in particular C₁ to C₄ alkyl, especially methyl or ethyl,n-propylisopropyl, n-butyl, sec-butyl, tent-butyl, cyclohexyl,2-ethylhexyl, octyl, decyl or lauryl. R₁, R₂, R₁₀, R₁₁, R₁₂ and R₁₃ mayespecially be methyl.

R₃ to R₉ may independently be selected from the group described for R₁,R₂, R₁₀, R₁₁, R₁₂ and R₁₃ or additionally OC_(n)H_(2n+1), (where n is aninteger from 1 to 20), NO₂, CN or O═CR (where R=alkyl, benzyl PhCH₂ or asubstituted benzyl, preferably a C₁ to C₂₀ alkyl, especially a C₁ to C₄alkyl).

Furthermore, the compounds may exhibit a chiral centre α to one of thenitrogen groups. This allows the possibility for polymers havingdifferent stereochemistry structures to be produced.

Compounds of general Formula 3 may comprise one or more fused rings onthe pyridine group.

One or more adjacent R₁ and R₃, R₃ and R₄, R₄ and R₂, R₁₀ and R₉, R₈ andR₉, R₈ and R₇, R₇ and R₆, R₆ and R₅ groups may be C₅ to C₈ cycloalkyl,cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclicaryl, such ascyclohexyl, cyclohexenyl or norborneyl.

The diimine compounds are preferably covalently attached to the supportvia positions R1, R2, R9, R10, R11, R12 or R13. They maybe attached viaa linkage group, such as a Schiff base to the support.

Preferred diimines include:

where: * indicates a chiral centre.

R14=Hydrogen, C₁ to C₁₀ branched chain alkyl, carboxy- or hydroxy-C₁ toC₁₀ alkyl.

The ligands, according to the first aspect of the invention, may be usedto from a catalyst for the addition polymerization of olefinicallyunsaturated monomers by using them in conjunction with:

a) a compound of formula 30

 MY

where M is a transition metal in a low valency state or a transitionmetal in a low valency state co-ordinated to at least one co-ordinatingnon-charged ligand and Y is a monovalent or polyvalent counterion; and

b) an initiator compound comprising a homolytically cleavable bond witha halogen atom.

Homolytically cleavable means a bond which breaks without integralcharge formation on either atom by homolytic fission. Conventionallythis produces a radical on the compound and a halogen atom radical. Forexample:

However, the increase in the rate of reaction observed by the inventorswith free-radical inhibitor indicates that true free-radicals are notnecessarily formed using the catalysts of the invention. It is believedthat this possibly occurs in a concerted fashion whereby the monomer isinserted into the bond without formation of a discrete free radicalspecies in the system. That is during propagation this results in theformation at a new carbon-carbon bond and a new carbon-halogen bondwithout free-radical formation. The mechanism possibly involves bridginghalogen atoms such as:

where:

ML is a transition metal-diimine complex.

A “free-radical” is defined as an atom or group of atoms having anunpaired valence electron and which is a separate entity without otherinteractions.

Transition metals may have different valencies, for example Fe(II) andFe(III), Cu(I) and Cu(II), a low valency state is the lower of thecommonly occurring valencies, i.e. Fe(II) or Cu(I). Hence M in Formula30 is preferably Cu(I), Fe(II), Co(II), Ru(II), Rh(I) or Ni(II), mostpreferably Cu(I). Preferably the coordinating ligand is (CH₃CN)₄. Y maybe chosen from Cl, Br, F, I, NO₃, PF₆, BF₄, SO₄, CN, SPh, SCN, SePh ortriflate (CF₃SO₃). Copper (I) triflate may be, which may be in the formof a commercially available benzene complex (CF₃SO₃Cu)₂C₆H₆. Theespecially preferred compound used is CuBr.

Preferably the second component (b) is selected from:

where R is independently selectable and is selected from straight,branched or cyclic alkyl, hydrogen, substituted alkyl, hydroxyalkyl,carboxyalkyl or substituted benzyl. Preferably the or each alkyl,hydroxyalkyl or carboxyalkyl contains 1 to 20, especially 1 to 5 carbonatoms.

X is a halide, especially I, Br, F or Cl.

The second component (b) may especially be selected from Formulae 43 to52:

where:

X=Br, I or Cl, preferably Br

R′=—H,

—(CH₂)_(p)R″ (where m is a whole number, preferably p=1 to 20, morepreferably 1 to 10, most preferably 1 to 5, R″=H, OH, COOH, halide, NH₂,SO₃, COX— where X is Br, I or C) or:

R₁₁₁=—COOH, —COX (where X is Br, I, F or Cl), —OH, —NH₂ or —SO₃H,especially 2-hydroxyethyl-2′-methyl-2′-bromopropionate.

Especially preferred examples of Formula 45 are:

Br may be used instead at Cl in Formulae 46A and 46B.

The careful selection of functional alkyl halides allows the productionof terminally functionalised polymers. For example, the selection of ahydroxy containing alkyl bromide allows the production of α-hydroxyterminal polymers. This can be achieved without the need of protectinggroup chemistry.

The transition metal may be precoordinated to the ligand covalentlyattached to its support.

Accordingly a second aspect of the invention provides a catalyst for usein the addition polymerisation of olefinically unsaturated monomers;especially vinyl monomers comprising a compound of general formula:

[(SD)_(c)M]^(d+)A  Formula 52

where:

M=a transition metal in a low valency state or a transition metalco-ordinated to at least one co-ordinating non-charged ligand,

S=a support,

D=a compound attached to the support, the compound being capable ofcomplexing with a transition metal,

d=an integer of 1 or 2,

c=an integer of 1 or 2,

A=a monovalent or divalent counter ion, such as Cl, Br, F, I, NO₃, PF₆,BF₄, SO₄, CN, SPh.

Preferably M is a defined for Formula 30 above. S may be as defined forFormula 1.

D may be adsorbed or covalently attached to the support.

D may be a compound as described earlier for the first aspect of theinvention.

D may have one of the nitrogens as not part of a diimine ring.

D may be a diimine according to Formulae 2-29 as previously defined.

Preferably the catalyst is used with an initiator comprising ahomolytically cleavable bond with a halogen atom, as previously defined.Preferred initiators are those defined in the first aspect of theinvention according to Formulae 31 to 53.

A third aspect of the invention provides a process for the production ofcompound such as diimine covalently attached to supports, according tothe first or second aspects of the invention.

The invention provides a process for producing a ligand for use in thecatalysis of addition polymerisation of olefinically unsaturatedmonomers, especially vinylic monomers, comprising the steps of:

(a) providing a primary amine functionalised support;

(b) providing a ligand precusor comprising an aldehyde group or ketonegroup; and

(c) reacting the primary amine functionalised support with the ligandprecursor to form a diimine compound covalently attached to the support.

The primary amine of the functionalised support reacts with the aldehydegroup or ketone group to form a Schiff base. Accordingly the diimine maybe produced by providing a ligand precursor with an aldehyde or ketonegroup replacing one of the imine groups of the final product, thereaction with the primary amine producing the second imine group. Thisis shown in the reaction scheme below which shows the reaction of asupport functionalised with a primary amine with 2-pyridine carbaldehydeto form a diimine attached to the support according to the first aspectof the invention. This can then be mixed with copper bromide or copperchloride to form a catalyst according to the second aspect of theinvention.

Alternatively an aldehyde or a ketone group may be provided separatelyon a diimine ligand precursor. Such a suitable precursor is shown inFormula 53

This allows the diimine to be decoupled from the support to allowcontrolled polymerisation.

Alternatively the following reaction scheme may be followed:

The primary amine group may alternatively be provided on the ligandprecursor and reacted with a ketone or aldehyde functionalised support.

The support material may be functionalised inorganic material, such assilica, especially silica gel. Alternatively functionalised organicsupport, especially a functionalised cross-linked polymeric support,such as poly(styrene-w-divinylbenzene) may be used. Such supports arepreferably usually used for absorbing compounds or in chromatography.

Preferably the reaction to form the Schiff base occurs at roomtemperature.

Preferably the functionalised support is an aminopropyl functionalsilica and the ligand precursor is 2-pyridine carbaldehyde.

The supported ligands and supported catalysts of the invention may beused in batch reactions or in continuous reactions to polymeriseolefinically unsaturated monomers. In the latter case, the supportedcatalyst or ligand may be packed into columns and the reaction mixturepassed through.

The supported ligand or supported catalyst may be conveniently removedfrom a reaction mixture by, for example, filtration, precipitation orcentrifugation. Alternatively the support may be magnetised beads andthe catalyst is removed by means of a magnet.

The invention also provides the use of the catalyst according to thefirst or second aspect of the invention in the addition polymerisationof one or more olefinically unsaturated monomers and the polymerisedproducts of such processes.

The components may be used together in any order.

The inventors have unexpectedly found that the catalyst will work at awide variety of temperatures, including room temperature and as low as−15° C. Accordingly, preferably the catalyst is used at a temperature of−20° C. to 200° C., especially −20° C. to 150° C., 20° C. to 130° C.,more preferably 90° C.

The olefinically unsaturated monomer may be a methacrylic, an acrylate,a styrene, methacrylonitrile or a diene such as butadiene.

Examples of olefinically unsaturated monomers that may be polymerisedinclude methyl methacrylate, vinylacetate, vinyl chloride acylonitonile,methacylamide, acrylamide, ethyl methacrylate, propyl methacrylate (allisomers), butyl methacrylate (all isomers), and other alkylmethacrylates; corresponding acrylates; also functionalisedmethacrylates and acrylates including glycidyl methacrylate,trimethoxsysilyl propyl methacrylate, allyl methacrylate, hydroxyethylmethacrylate, hydroxypropyl methacrylate, dialkylaminoalkylmethacrylates; fluoroalkyl (meth)acrylates; methacrylic acid, acrylicacid; fumaric acid (and esters), itaconic acid (and esters), maleicanhydride; styrene, α-methyl styrene; vinyl halides such as vinylchloride and vinyl fluoride; acrylonitrile, methacrylonitrile;vinylidene halides of formula CH₂═C(Hal)₂ where each halogen isindependently Cl or F; optionally substituted butadienes of the formulaCH₂═C(R₁₅)C(R¹⁵)═CH₂ where R¹⁵ is independently H, C₁ to C₁₀ alkyl, Cl,or F; sulphonic acids or derivatives thereof of formula CH₂═CHSO₂OMwherein M is Na, K, Li, N(R¹⁶)₄ where each R¹⁶ is independently H or C₁to C₁₀ alkyl, D is COZ, ON, N(R¹⁶ )₂ or SO₂OZ and Z is H, Li, Na, K orN(R¹⁶)₄; acrylamide or derivatives thereof of formula CH₂═CHCON(R¹⁶)₂;and methacryiamide or derivative thereof of formula CH₂═C(CH₃)CON(R¹⁶)₂.Mixtures of such monomers may be used.

Preferably, the monomers are commercially available and may comprise afree-radical inhibitor such as 2,6-di-tert-butyl-4-methylpenol ormethoxyplenol.

Preferably the co-catalysts are used in the ratios 0.01 to 1000 D: MY,preferably 0.1 to 10, and compound MY: initiator 0.0001 to 1000,preferably 0.1 to 10, where the degree of polymerisation is controlledby the ratio of monomer to (b) (expressed as molar ratios).

Preferably the components of the catalyst of the second aspect of theinvention are added at a ratio M:initiator of 3:1 to 1:100.

Preferably the amount of diimine: metal used in the systems is between1000:1 and 1:1, especially, 100:1 and 1:1, preferably 5:1 to 1:1, morepreferably 3:1 to 1:1.

The ratio of RX:Copper is 1000:1 to 1:1, especially 100:1 to 1:1.

The reaction may take place with or without the presence of a solvent.Suitable solvents in which the catalyst, monomer and polymer product aresufficiently soluble for reactions to occur include water, protic andnon-protic solvents including propionitrile, hexane, heptane,dimethoxyethane, diethoxyethane, tetrahydrofuran, ethylacetate,diethylether, N,N-dimethylformamide, anisole, acetonitrile,diphenylether, methylisobutyrate, butan-2-one, toluene and xylene.Especially preferred solvents are xylene and toluene, preferably thesolvents are used at at least 1% by weight, more preferably at least 10%by weight.

Preferably the concentration of monomer in the solvents is 100% to 1%,preferably 100% to 5%.

The reaction may be undertaken under an inert atmosphere such asnitrogen or argon.

The reaction may be carried out in suspension, emulsion, mini-emulsionor in a dispersion.

Statistical copolymers may be produced using the catalysts according tothe invention. Such copolymers may use 2 or more monomers in a range ofca.0-100% by weight of each of the monomers used.

Block copolymers may also be prepared by sequential addition of monomersto the reaction catalyst.

Telechelic polymers, may be produced using catalysts of the invention.For example, a functional initiator such as Formula 21 may be used withtransformation of the w-Br group to a functional group such as —OH or—CO₂H via use of a suitable reactant such as sodium azide.

Comb and graft copolymers may be produced using the catalysts of theinvention to allow, for example, polymers having functional side chainsto be produced, by use of suitable reagents.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will now be described by way of example andwith reference to the following figure:

FIG. 1 show the polymerisation of methylmethacrylate for four monomeradditions to supported catalyst which has been collected at the end ofeach previous polymerisation reaction.

FIG. 2 shows infrared spectra for the stepwise synthesis of pyridylligand onto cross-linked polystyrene beads.

FIG. 3 shows kinetic reproducibility of silica supported atom transferpolymerisation from experiments carried out with different silicasupported ligands synthesised at different times.

FIG. 4 shows recycling experiments carried out with support S4 using thesame conditions:

[MMA]:[Cu]:[Si-lig]:[E2 BI]=100:1:3:1

FIG. 5 shows reinitiation of PMMA.

DETAILED DESCRIPTION OF THE INVENTION

Reagents:

Methyl methacrylate (Aldrich, 99%) was purified by passing through acolumn of activated basic alumina to remove inhibitor. Copper(I) bromide(Aldrich, 98%) was purified according to the method of Keller & Wycoff.Toluene (Fisons, 99.8%) was dried over sodium. Ethyl-bromoisobutyrate(Aldrich, 9%), 2-pyridene carboxaldehyde, 3-aminipropyl-functionalisedsilica gel (Aldrich, 98% functionalised), silica gel (Merck), anddiethyl ether (BDH, 98%) were used as received.

Ref: Keller, R. N.; Wycoff, H. D. Inorg. Synth. 2,1 (1946)

Characterisation:

Conversion was measured by gravimetry, and molecular weightdistributions were measured using size exclusion chromatography (SEC) ona system equipped with a guard column, a mixed E column (PolymerLaboratories) and a refractive index detector, using tetrahydrofuran at1 mL.min⁻¹ as an eluent. Poly(MMA) standards in the range (10⁶-200g.mol⁻¹) were used to calibrate the SEC.

SiO₂ Supported Catalyst-covalently Bound Schiff Bases EXAMPLE 1

2-pyridine carboxaldehyde (0.714 g, 6.67×10⁻³ mol) was added to3-aminopropylfunctionalised silica gel (3.00 g, 3.15×10⁻³ mol of activeNH₂) dispersed in diethyl ether (50 mL) and stirred for 1 hr. Thediethyl ether was removed and the ligand functionalised silica gelwashed with two aliquots of diethyl ether (50 mL), and dried undervacuum. The ligand functionalised silica gel was added to a Schlenkflask and purged with nitrogen. To this, a solution of toluene (30 g),MMA (10 g) and ethyl 2-bromoisobutyrate (0.138 g) that was degassed bythree freeze-pump-thaw cycles, was added. This was followed by theaddition of copper(I) bromide (0.144 g). The addition copper(I) bromideresults in the SiO₂ supported catalyst. Agitation was effected by amagnetic stirrer. The mixture was then placed in an oil bath at 90° C.to commence reaction. Samples were taken periodically for conversion andmolecular weight analysts. After approximately 20 hr the mixture wascooled to room temperature and the SiO₂ supported catalyst allowed tosettle. The polymer solution was removed via cannula, and the SiO₂supported catalyst washed with two aliquots of toluene (50 mL). To this,another solution of toluene, MMA and ethyl 2-bromoisobutyrate was added(concentrations as per previous solution) and the mixture placed in oilbath at 90° C. This procedure was repeated for two more monomeradditions, demonstrating that the SiO₂ supported catalyst could be usedat least four times for consecutive reactions. The results are shown intable 1 and FIG. 1.

Poly(stryene-w-divinylbenzene) Supplied Catalyst-covaltently BoundSchiff Base EXAMPLE 2

2-pyridine carboxaldehyde (0.5 g, 6.67×10⁻³) was added toaminofunctionalised cross-linked polystryene beads (1.30 g) dispersed intetrahydrofuran (50 mL) and stirred for 1 hr. The tetrahydrofuran wasremoved and the ligand functionalised polystryene beads washed with twoaliquots of tetrahydrofuran (50 mL) and dried under vacuum. The ligandfunctionalised polystryene was added to a Schlenk flask and purges withnitrogen. To this, a solution of toluene (12 g), MMA (4.0 g) and ethyl2-bromoisbutyrate (0.075 g), that was degassed by three freeze-pump-thawcycles, was added. This was followed by the addition of copper(I)bromide (0.057 g). The addition copper(I) bromide produced thepolystyrene supported catalyst. Agitation was effected by a magneticstirrer. The mixture was then placed in an oil bath at 90° C. tocommence reaction. Samples were taken periodically for conversion andmolecular weight analysis. After approximately 20 hr the mixture wascooled to room temperature and the polystyrene supported catalystallowed to settle. The polymer solution was removed via cannula. Theresults are shown in table 1 and FIG. 2.

SiO₂ Adsorbed Catalyst EXAMPLE 3

A solution of toluene (21 g), MMA (7.1 g), ethyl 2-bromoisobutyrate(0.139 g) and N-^(n)octyl pyridylmethanimine (0.465 g) that was degassedby three freeze-pump-thaw cycles, was added to Schlenk flask containingsilica gel (3.0 g).

To this, copper(I) bromide (0.095 g) was added. Agitation was effectedby a magnetic stirrer. The mixture was then placed in an oil bath at 90°C. to commence reaction. Samples were taken periodically for conversionand molecular weight analysis. After approximately 20 hr the mixture wascooled to room temperature and the SiO₂ adsorbed catalyst allowed tosettle. The polymer solution was removed via cannula. The results areshown in table 1.

SiO₂ Adsorbed Catalyst (II)—Non Covalently Bound on Amino FunctionalisedSilica EXAMPLE 4

A solution of toluene (21 g), MMA (7.1 g), ethyl 2-bromoisobutyrate(0.139 g) and N-^(n)octyl pyridyimethamine (0.465 g) that was degassedby three freeze-pump-thaw cycles was added to Schlenk flask containing3-aminopropyl-functionalised silica gel (3.0 g). To this, copper(I)bromide (0.095 g) was added. Agitation was effected by a magneticstirrer. The mixture was then placed in an oil bath at 90° C. tocommence reaction. Samples were taken periodically for conversion andmolecular weight analysis. After approximately 20 hr, the mixture wascooled to room temperature and the SiO₂ adsorbed catalyst allowed tosettle. The polymer solution was removed via cannula. The results areshown in table 1.

TABLE 1 Conver- Example Time/Hr sion Mn Mw PDI 1A 1.33 0.458 21400 458002.14 1B 20 0.98 21000 45600 2.18 1C 26 — — — — 1D 28 0.38 13600 404002.97 1E 30.5 0.726 18600 44600 2.39 1F 45 0.976 18700 46300 2.48 1G49.25 — — — — 1H 51.75 0.149 25000 46100 1.85 1I 70 0.942 24800 496002.00 1J 77.25 — — — — 1K 77.83 0.031 21200 38500 1.81 1L 78.75 0.08518300 37300 2.03 1M 92.5 0.760 11200 32200 2.87 2A 1 0.388  9030 176001.95 2B 2.33 0.681 11500 18900 1.64 2C 3.58 0.876 12800 21300 1.67 2D17.92 0.986 13300 22600 1.70 3A 1 0.446  8950 15000 1.67 3B 2.33 0.66610600 17000 1.61 3C 3.58 0.753 10200 15200 1.50 3D 17.92 0.817 1060015800 1.50 4A 1 0.702 11400 20200 1.76 4B 2.33 0.891  5970 19700 3.31 4C3.58 0.906 11800 21100 1.79 4D 17.92 0.922 11300 20800 1.84 Time Conver-(min) sion (%) M_(n) M_(w) PDi 5A 120 59  8600 15400 1.78 5B 300 83 9700 15600 1.61 5C 1380 96 11300 19200 1.70

EXAMPLE 5 Ru(PPh₃)₃Cl₂ on 3-Aminopropyl-functionalised Silica Gel

0.14 g Ru(PPh₃)₃ (1.461×10⁻⁴ mol) together with 0.558 g (5.84×10⁻⁴ mol)3-aminopropyl-functionalised silica gel (˜9% functionalised; ˜1.05 mmolNH₂/gram) was added to a schlenk and subjected to three vacuum-argoncycles. To this mixture was added 1.5 ml degassed MMA (1.395×10⁻² mol)and 5 ml degassed xylene and the mixture heated to 96° C. and stirred.The polymerisation reaction was initiated by the addition ofethyhl-2-bromoisobutyrate, 0.021 ml (1.430×10⁻⁴ mol), and the timer wasstarted.

Samples were removed at regular intervals and the percentage conversionand molecular weight of the product polymer determined (conversions wereby ¹H NMR).

EXAMPLE 6 RuCl₃ on 3-Aminopropyl-functionalised Silica Gel

0.095 g RuCl₃ 4.65×10⁻⁶ mol) together with 1.86 g (1.395×10⁻³ mol)3-aminopropyl-functionalised silica gel (˜9% functionalised; ˜1.05 mmolNH₂/gram) was added to a schlenk and subjected to three vacuum/argoncycles. To this mixture was added 5 ml degassed MMA (4.65×10⁻² mol) and15 ml degassed xylene and the mixture heated to 90° C. and stirred. Thepolymerisation reaction was initiated by the addition of ethyl2-bromoisobutyrate, 0.069 ml (4.65×10⁻⁴ mol), and the timer was started.

Time (min) Conversion % Mn Mw PDi 6A  120 6.9 209000 336000 1.61 6B  30015.1 192000 341000 1.775 6C 1380 74.2  84700 225000 2.65

EXAMPLE 7 RhCl₃ (H₂O)₃ on 3-Aminopropyl-functionalised Silica Gel

0.122 g RhCl₃(H₂O)₃ (4.65×10⁻⁴ mol) together with 1.86 g (1.395×10⁻³mol) 3-aminpropyl-functionalised silica gel (˜9% functionalised; ˜1.05mmol NH₂/gram) was added to a schlenk and subjected to three vacuumargon cycles. To this mixture was added 5 ml degassed MMA (4.65×10⁻²mol) and 15 ml degassed xylene and the mixture heated to 90° C. andstirred. The polymerisation reaction was initiated by the addition ofethyl-2-bromoisobutyrate, 0.069 ml (4.65×10⁻⁴ mol), and the timer wasstarted.

Time (min) Conversion Mn Mw PDi 7A  120 6.1 93600 314000 3.35 7B  30021.5 17900 320000 1.78 7C 1380 68.7 89100 243000 2.72

EXAMPLE 8 Ag(CF₃CO₃) on 3-Aminopropyl-functionalised Silica Gel

0.10 g Ag(CF₃CO₂) (4.65×10⁻⁴ mol) together with 1.86 g (1.395×10⁻³ mol)3-aminoproply-functionalised silica gel (˜9% functionalised; ˜1.05 mmolNH₂/gram) was added to a schlenk and subjected to three vacuum/argoncycles. To this mixture was added 5 ml degassed MMA (4.65×10⁻² mol) and15 ml degassed xylene and the mixture heated to 90° C. and stirred. Thepolymerisation reaction was initiated by the addition of ethyl2-bromoisobutyrate, 0.069 ml (4.65×10⁻⁴ mol) and the timer was started.

Time (min) Conversion Mn Mw PDi 8A  120 2.6  61200 226000 3.68 8B  30013.4 149000 324000 2.18 8C 1380 41.8 148000 299000 2.01

The precursor shown to Formula 53 may be produced by reacting 2-pyridinecarbaldehyde with an α-aminocarboxylic acid, such as 8-amino caprylicacid, followed by mild reduction or by coupling of the parent acidthrough an amide link. It is envisaged that the use of amino acids willallow the incorporation of asymetry into the system.

Synthesis of Polystyrene Support

The pyridyl route

TABLE Comparison of synthesis techniques and characterisation ofpolystyrene supports synthesized via the pyridyl route. n ligand/g nCu/g by % retention Step 1 Step 1 by NMR ICP between ICP n^(o) type part1* part 2** Step 2*** (% vs th) (% vs theory) and NMR PS1 PS 1 1 1 1.75× 10⁻³ 1.38 × 10⁻³ 98.5 (55.7) (63.5) PS2 PS 1 2 2 2.32 × 10⁻³ 5.82 ×10⁻⁴ 33.4 (71) (26.8) PS3 PS 2 2 2 3.09 × 10⁻³ ? ? (98.5) PS4 PSm 2 3 21.27 × 10⁻³ ? ? (40.4) PS5 PSp 2 2 2 2.84 × 10⁻³ ? ? (90.7) PS6 PSp 2 22 2.77 × 10e⁻³ 1.39 × 10⁻³ 87.8 (88.6) (80.6) PS7 PSp 2 2 2 2.94 × 10⁻³1.44 × 10⁻³ 69.9 (94) (66.9) *Step 1-part 1: 1 = DMF, 50° C.; 2 = DMF,110° C. **Step 1-part 2: 1 = DMF, RT; 2 = EtOH, 80° C.; 3 = DMF, 90° C.***Step 2: 1 = Et2O, RT; 2 = Toluene, 130° C., soxhlet; 3 = Toluene, RT

Analysis of Support

TABLE Infrared peak assignments for polystyrene supported ligandssynthesised following the pyridyl route functional IR peak assignmentSupport type groups (cm⁻¹) A chloromethylated CH2—Cl 1250 B PhthalimidoC═O 1710, 1770 functions C amino functions NH2 1630, 3200 D ligandfunctions C═N 1490, 1600, 1660

FIG. 2 shows infrared spectra for the stepwise synthesis of the pyridylligand onto cross-linked polystyrene beads.

Typical Procedure for the Synthesis of Support PSS, PS6 and PS7

Step 1-Part1: Plthalimidomethylated Cross-linked Polystyrene Beads (B)

To a stirred suspension of cross-linked chloromethylated beads (3 g, 12mmol) in DMF (100 ml) was added potassium phthalimide (11.19 g, 60.4mmol) and the reaction mixture was heated at 110° C. for 7 h. Aftercooling, toluene (100 ml) was added and the reaction mixture wasfiltrated then washed with water (100 ml), methanol (100 ml) and diethylether (100 ml). The solid was dried under vacuum at RT for one day, thenat 60° C. overnight in a vacoven. Product: white solid (4.15 g).

IR absorption: 1710, 1770 cm−1(v C═O). Elemental analysis: 80.64% C,5.85% H, 3.49% N (theoretical; 81.43% C, 5.82% H, 3.88% N).

Step 1-Part 2: Aminomethylated Cross-linked Polystyrene Beads (C)

To a stirred suspension of phthalimide derivative (4.07 g, 16.3 mmol) inethanol (150 ml) was added hydrazine monohydrate (4.6 ml, 0.147 mol).The reaction mixture was heated at 80° C. for 3 h then cooled to roomtemperature and left overnight (careful, once the hydrazine has beenadded, you need enough solvent to compensate the swelling of the beads).Then the reaction mixture was filtered and the solid washed with water(100 ml), methanol (50 ml) and diethyl ether (50 ml). The solid wasdried under vacuum at RT for one day, then at 60° C. overnight in avacoven. Product: white solid (3.24 g).

IR absorption: 1650, 1600, 1490 cm−1 (v N—H?). Elemental analysis:76.61% C, 6.56% H, 8.48% N (theoretical; 85.7% C, 8.22% H, 6.06% N).

Step 2: Pyridiniminemthylated Cross-linked Polystyrene Beads (D)

To a suspension of amino derivated support C (1.94 g, 7.74 mmol NH₂) intoluene (50 ml) was added pyridine carbaldehyde (1.661 g, 15.3 mmol).The mixture was heated under reflux (130° C.) in a soxhlet extractor inwhich the thimble contained 3A molecular sieves. The support was removedby filtration and washed successively with THF (50 ml), methanol (50 ml)and diethyl ether (50 ml) to give, after drying under reduced pressureat RT and 60° C. overnight to constant weight, an orange solid (2.18 g).

IR absorption: 1650, 1600, 1490cm−1 (v C═N). Elemental analysis: 81.06%C, 6.5% H, 8.05% N (theoretical; 84.36% C, 6.88% H, 8.75% N).

The (di)Amine Route

TABLE Summary of cross-linked polystyrene supports synthesised followingthe (di)amine route. Amine func- tion- n ligand/g by Support Aminealisation NMR Support code used reaction ( % vs th) E PS-EDA-ligethylene diamine DA1 2.75 e⁻³ (99.7) F PS-DETA-lig diethylene triamineDA1 4.02 e⁻³ (99.5) G PS-TAEA-lig tris(2-aminoethyl)- DA3 2.63 e⁻³ amine(70.8) H PS-HEMDA-lig hexamethylene- DA2 ? diamine

Procedure for Synthesis of PS Supports Following the (di)Amine Route

Synthesis DA1: (Supports E & F)

A suspension of chloromethylated cross-linked polystyrene beads (3 g, 4mmol of Cl/g resin, 12 mmol) was shaken in round bottom flask with 15 mlamine during one day at room temperature. The polymer was filtered andsuccessively rinsed two times with 10% trietylamine indimethylformamide, once with DMF, four times with 10% Et3N intetrahydrofuran, three times with THF and three times with methanol. Thesolid was then dried under vacuum at RT then at 80° C. in the vacoven toconstant weight.

Synthesis DA2: (Support H)

Same as DA1 but the amine is mix with 100 ml DMF in order to solubilisedit.

Synthesis DA3: (Support G)

A suspension of chloromethylated cross-linked polystyrene beads (3 g, 4mmol of Cl/g resin, 12 mmol) in DMF (100 ml) was shaken in round bottomflask with tris(2-aminoetyl)amine (5 ml, 33.4 mmol) for 6 h at 65° C.under N2 atmosphere. After cooling to room temperature, the resin wasfiltered and washed successively with two times with 10% triethylaminein dimethylformamide, once with DMF, four times with 10% Et3N intetrahydrofuran, three times with THF and three times with methanol. Thesolid was then dried under vacuum at RT then at 80° C. in the vacoven toconstant weight.

The amino-hexanol route of pyridine carbaldehyde, leading to the spacedsupported ligand.

Scheme. Two different ways to the synthesis of hexenoxy supported ligand

TABLE Functionalisation of supports synthesised following theamino-hexanol route n ligand/g by NMR n Cu/g by ICP % retention betweenSupport (% vs th) (% vs theory) ICP and NMR K1 2.13 × 10⁻³ 1.43 × 10⁻³87.6 (90) (80.5) K2 2.16 × 10⁻³ 1.12 × 10⁻³ 68 (91) (63.1) L ? 9.25 ×10⁻⁴ ? (52.1)

Procedure for Synthesis of Polystyrene Supports Via the Amino-hexanolRoute.

N-^(n)Hexanehydroxy-2-pyridine Methanimine (2):

6-Phthalimido-1-hexanol (5):

A solution of 6-amino-1-hexanol (7.54 g, 62.4 mmol) in 15 ml THF wasadded to a stirred slurry of N-(ethoxycarbonyl)phthalimide (14.08 g, 63mmol) in 50 ml THF at 0° C. (ice-water bath) with a pressure equalisingfunnel. After 5 minutes, the bath was removed and the mixture stirredovernight at ambient temperature. After removal of the solvent underreduce pressure, the compound was distillated (0.4 Torr) to give ethylcarbamate. The residue was put through a crystallisation procedure froma solution of toluene (25 ml) and hexane (10 ml) but the product stayedoily. The crystallisation started with scratching the product withspatula to give a light brown solid (13.9 g, 90% yield).

¹H NMR: δ=7.81, 7.71 (m, 4H); 3.61 (m, 4H); 2.3 (s, 1H); 1.68, 1.39(overlapping multiplets, 8H). Elemental analysis: 67.8% C, 6.9% H, 5.7%N (theoretical; 68% C, 6.93% H, 5.66% N),

Route A: Phthalimidohexanoxy methylated cross-linked polystyrene beads(I):

To a slurry of potassium hydride (0.81 g, 33.7 mmol) and tetrahydrofuran(100 ml) was added, with stirring, a solution of6-plithalimido-1-hexanol (5) (5.92 g, 23.9 mmol), dibenzo-18-crown-6(200 mg, 0.56 mmol) and hexamethylphosphoric triamide (10 ml). After 1hour at ambient temperature, a slurry of chloromethylated polystyrenebeads (3 g, 12 mequiv. Cl) in tetrahydrofuran (50 ml) was added. Thereaction mixture was stirred and heated under reflex for 48 hours. Thepolymer was separated by filtration and washed successively withsolutions of tetrahydrofuran/ethanol (1/1), tetrahydrofuran/methanol(1/1) and then with diethyl ether. The polymer was dried under reducepressure to constant weight to give a white solid (4.36 g, ˜60%).

IR absorption: 1710, 1770 cm−1 (v C═O),1075 cm−1 (v C—O—C).

Route A: Aminohexanoxy Methylated Cross-linked Polystyrene Beads (J):

Same procedure as for support C.

Route A: Pyridinimenehexanoxy Methylated Cross-linked Polystyrene Beads(K):

Same procedure as for support D.

IR absorption: 1650 cm−1 (v C═N).

Route B: Pyridiniminehexanoxy Methylated Cross-linked Polystyrene Beads(L):

Same procedure as for support I, replacing phthalimido-hexanol (5) byN-^(n)hexanehydroxy-2-pyridine methanimine (2).

IR absorption: 1650 cm−1 (v C═N).

Synthesis of Silica Support

Scheme. Two different silica supports synthesised by direct condensationof pyridine carbaldehyde onto the primary supported amine.

Supports S1 to S4 were found to be bright orange solids, although S5 waslight yellow and S6 beige. Supports S1 to S5 were easily complexingcopper bromide in methanol (black colour of the support). It took timeto notice a change of colour for S6, when trying to complex CuBr.

TABLE Comparison of synthesis routes and characterisation of silicasupported ligands. % retention Silica Step n ligand/g by NMR n Cu/g byICP between support 2^(a) (% vs th) (% vs theory) ICP and NMR S1  2^(b)1.04 e⁻³ 7.08 e⁻³ 84 (>100) (84)   S2 2 1.15 e⁻³ 7.92 e⁻⁴ 93.8 (>100)(93.8) S3 2 1.16 e⁻³ ? ? (>100) S4 2 1.16 e⁻³ 7.22 × 10⁻⁴ 85.6 (>100)(85.6) S5 3 9.88 e⁻³ ? ? (>100) S6 1 ? ? ? ^(a)Step 2: 1 = Et2O, RT; 2 =Toluene, 130° C., soxhlet, 3 = Toluene, RT ^(b)Step 2 method 2:Typically mixture of 3-aminopropyl silica gel (15 g, 15.75 mmol) intoluene (150 ml) with pyridine carbaldehyde (3.6 g, 33 mmol).

Silica Supported Atom Transfer Polymerisation

In a typical SSATP reaction, CuBr (0.134 g, 9.34×10⁻⁴ mol) and thesupport (x grams, depending on the experimentally calculated loading ofligand onto the support; [Si-lig]:[Cu]=n:1, where [Si-lig] is theconcentration of ligand anchored to the silica support and n=1, 2, 3, 4)were placed in a predried Schlenk flask which was evacuated and thenflushed with nitrogen three times. Deoxygenated toluene (20 ml, 66% v/v)and deoxygenated methyl methacrylate (10 mL, 9.36×10⁻² mol) were addedand the suspension stirred. The flask was heated in a thermostatted oilbath at 90° C. and when the temperature had equilibratedethyl-2-bromoisobutyrate (0.137 mL, 9.34×10⁻⁴ mol, [MMA]0:[In]0=100:1)was added. Samples (1-2 ml) were taken periodically after initiator wasadded. Conversions were calculated by gravimetry heating sample toconstant weight overnight at 90° C. under vacuum. The polymer was thendiluted in THF and passed through basic aluminum oxide in order toremove the copper catalyst which has gone into solution.

TABLE Silica Supported Atom Transfer Polymerisations of MMA in toluene[lig]/ Time Conv. Mn_(th) ^(d) Mn_((SEC)) Type^(a) Support^(b) [Cu](min) (%) (g/mol) (g/mol) PDI ATP1 / 2 60 15 1 500 3 430 1.14 360 80 8010 9 050 1.11 SS1 SiNH₂ ^(c) 1 60 13 1 300 18 2800 2.1 300 34 3 400 SS2SiNH₂ 2 60 19 1 900 300 52 5 200 146 300 1.94 SSATP S1 1 60 27 2 700 19700 1.63 1 360 67 6 700 18 500 1.8 SSATP S2 1 60 33 3 300 12 250 1.59 2360 75 7 510 15 950 1.56 SSATP S2 2 60 48 4 800 12 200 1.6 3 360 98 9810 14 900 1.68 SSATP S2bis 1 30 29 2 900 12 300 1.65 4 300 76 7 610 18200 1.64 SSATP S3 2 30 35 3 500 12 800 1.68 5 250 86 8 610 15 500 1.71SSATP S4 2 30 36 3 600 12 800 1.68 6 260 91 9 110 16 350 1.78 SSATP S5 230 30 3 000 18 900 2.1 7 300 91 9 110 16 500 2.1 SSATP S6 ? 60 40 4 00050 850 2.5 8 240 74 7 410 50 800 2.4 ^(a)further data are available^(b)See table V-7. ^(c)3-aminopropyl silica gel; here [lig] is equal tothe concentration of amine functions on the silica support.^(d)Mn_((th)) = ([M_(MMA)]₀/[I]₀ × MW_(MMA)) × conversion, whereMW_(MMA) is the molecular weight of methyl methacrylate and[M_(MMA)]₀/[I]₀ is the initial concentration ratio of MMA to initiator.

FIG. 3 shows kinetic reproducibility of silica supported atom transferpolymerisation from experiments carried out with different silicasupported ligands synthesised at different times.

Recycling Experiments

Recycling experiments, using the same support, have also been carriedout. Here, we present the results obtained when support S4 was used(some recycling experiments with support S2 are also available in§VI.3.2). A first polymerisation was carried out using 3 equivalents ofsilica supported ligand in reference to copper [MMA]:[Cu]:[Si-ligS4]:[E2BI]-100:1:3:1), then the solution medium was removed from theschlenk tube with a syringe. The support, still carrying the transitionmetal catalyst, was washed three times with degassed toluene introducedand removed from the tube by syringe. The support was then dried undervacuum. During all this procedure, the support stayed in the schlenktube and was kept under nitrogen in order to avoid any deactivation bycontact with air. The washed support was then reused for a newpolymerisation by introducing into the schlenk tube, in the followingorder: 20 ml of toluene, 10 ml of MMA and 0.137 ml of E2BI (samecondition as before: [MMA]:[Cu]:[Si-lig]:[E2BI]=100:1:3:1). Threerecycling polymerisations were experimented with the same support.

FIG. 4 shows recycling experiments carried out with support S4 using thesame conditions; [MMA]:[Cu]:[Si-lig]:[E2BI]=100:1:3:1

Each recycling experiment shows a decrease of the kinetic rate ofpolymerisation for MMA. However, recyclings 2 and 3 have the samekinetic behaviour. It seems that the catalyst activity is affected aftereach polymerisation. Probably, the amount of active species is reducedduring the time of the experiment and the time of the washing of thesupport. This degradation finds a limit after a certain time or acertain number of recyclings. The polydispersities still remain the same(around 1.7), even after several use of the support.

TABLE Recycling experiments carried out with support S4 for thepolymerisation of MMA by silica supported atom transfer polymerisation;[MMA]:[Cu]:[Si-lig]:[E2BI] 100:1:3:1 Time Conversion Mnth Mn(SEC)Experiment^(a) (min) (%) (g/mol) (g/mol) PDI First polym.  30 41 410011600 1.76 180 90 9010 13800 1.8 Recycling 1 130 43 4300 1900 1.75 33081 8110 16850 1.69 Recycling 2 130  8  800 360 57 5700 17100 1.69Recycling 3 130  8  800 ? ? 310 43 4300 17200 1.7

Influence of initiator and solvent on silica supported atom transferpolymerisation of MMA

TABLE Influence of initiator and solvent on silica supported atomtransfer polymerisation of MMA [lig]/ Conv. Mn_(th) ^(c) Mn_((SEC))Support [Cu] Initiator^(b) Solvent % (6 h) (g/mol) (g/mol) PDI S1 1 E2BIToluene 67 6 500 18 500 1.79 S1 1 DPB Toluene 25 2 500 8 300 1.74 S1 1TS Toluene 38 3 800 9 200 1.74 S1 1 E2BI Anisole 60 6 000 14 250 1.68 S11 E2BI Phe₂O 84 8 410 17 580 1.71 ^(b)E2BI: ethyl-2-bromoisobutyrate;DPB: 1,1,1-diphenyl methyl bromide; TS: tosyl bromide ^(c)Mn_((th)) =([M_(MMA)]₀/[I]₀ × conversion, where MW_(MMA) is the molecular weight ofmethyl methacrylate and [M_(MMA)]₀/[I]₀ is the initial concentrationratio of MMA to initiator.

Ruthenium Supported Atom Transfer Polymerisation

Typical Polymerisation Procedure

In a typical reaction, for example [In]:[Ru]:[SiNH2]=1:1:2, theruthenium RuCl2(PPh3)3 (˜0.45 g, 4.69×10⁻⁴ mol) and the support (˜0.90g, 9.49×10⁻⁴) are introduced in a schlenk tube and subjected to threevacuum/nitrogen cycles. Deoxygenated toluene (15 ml, 75% v/v) anddeoxygenated methyl methacrylate (5 ml, 4.67×10⁻² mol) were added andthe suspension stirred. The flask was heated in a thermostatted oil bathat 90° C. and when the temperature had equilibratedethyl-2-bromoisobutyrate (0.069 mL, 4.69×10⁻⁴ mol, [MMA]0:[In]0=100:1)was added. Samples (1-2 ml) were taken approximately 15, 30, 60, 120,180, 240 and 300 minutes after initiator was added. Conversions werecalculated by gravimetry heating sample to constant weight overnight at90° C. under vacuum. The polymer was then diluted in THF and passedthrough basic aluminum oxide in order to remote the ruthenium catalystwhich has gone into solution.

TABLE Molar ratios of components used in Silica supported-Rutheniummediated-ATP Experiment [MMA] [E2BI] [RUCl₂(PPh₃)₃] [support]^(a) 1 1002 1 4 2 100 1 1 4 3 100 0.5 1 4 4 100 1 2 8 5 100 1 0.5 2 6 100 1 1 8 7100 1 1 2 8 100 1 0.5 silica^(b) 9 100 1 0.5 Al₂O₃ ^(c) 10^(d) 100 2 1 4^(a)concentration of NH₂ on 3-aminopropyl functionalised silica gel^(b)silica gel ^(c)basic alumina ^(d)reused the catalyst from experiment1

TABLE Results for silica supported-ruthenium medicated-ATP (SS-Ru-ATP)Experi- Conversion Mnth Mn ment t(min) (%) (g/mol) (g/mol) PDI 1 30 341700 5040 1.82 180 90 4550 6780 1.56 2 30 40 4000 6750 1.76 180 93 926010700 1.5 3 30 35 7040 10300 1.74 240 91 18200 21500 1.49 4 30 46 46006530 1.56 180 98 9810 11250 1.54 5 30 23 2330 6420 1.97 180 78 777010500 1.55 6 30 39 3900 8000 3.1 120 88 8850 11300 2.22 7 30 26 26005280 1.50 180 75 7510 8380 1.47 8 45 18 1800 5780 1.51 240 42 4220 78501.67 9 45 22 2200 5850 1.59 180 40 4000 7240 1.57 10  30 25 1250 49302.14 240 88 4400 6770 1.73

Reinitiation Experiments

In order to confirm the living character of this polymerisation,reinitiations from previously synthesised PMMA (made by silicasupported-ruthenium mediated-ATP: SS-Ru-ATP) have been carried out. Twotypes of macroinitiators PMMA1 and PMMA2 have been synthesised followingthe conditions from experiments 4 and 7 respectively. They have beenused for initiation of MMA and BzMA by SS-Ru-ATP, keeping the samecatalyst and support quantities.

TABLE molar ratios of components used in silica supported-rutheniummediated-ATP reinitiation experiments Experi- Macroinitiator^(a) Monomer2 ment ([m]) ([M]) [RUCl(PPh3)3] [support]^(b) 11 PMMA1 MMA 2 8 (0.317)(100) 12 PMMA1 BzMA 2 8 (0.317)  (63) 13 PMMA2 MMA 1 2 (0.338) (100) 14PMMA2 BzMA 1 2 (0.338)  (63) ^(a)PMMA1 synthesised following conditions[E2BI]:[Ru]:[NH2]= 1:2:8, experiment 4 PMMA2 synthesised followingconditions [E2BI]:[Ru]:[NH2]= 1:1:2, experiment 7 ^(b)concentration ofNH2 on 3-aminopropyl functionalised silica gel

TABLE Data for SS-Ru-ATP macroinitiation experiments using differentmonomers Experi- Macr Time Conv % Mnth Mnexp ment targeted (min) 2^(nd)pol° (g/mol) (g/mol) PDI 11 41600 0 0 10083 1.37 30 30 20162 15230 1.57285 85 36736 31013 2.62 12 45040 0 0 10083 1.37 30 60 30548 23262 1.60180 95 43297 37105 1.88 13 39080 0 0  9465 1.26 30 30 18079 14282 1.37330 95 37147 29369 1.48 14 42280 0 0  9465 1.26 30 55 27113 18132 1.35200 90 39535 26969 1.35

Polystyrene Supported Atom Transfer Polymerisation

Typical Polymerisation Procedure

In a typical PS-SATP reaction, CuBr (0.134 g, 9.34×10⁻⁴ mol) and thesupport (x grams, depending on the experimentally calculated loading ofligand onto the support; [PS-lig]:[Cu]=n:1, where [PS-lig] is theconcentration of ligand anchored to the polystyrene support and n=1, 2,3, 4, etc. . . . ) were placed in a predried Schlenk flask which wasevacuated and then flushed with nitrogen three times. Decoxygenatedtoluene (20 ml, 66% v/v) and deoxygenated methyl methacrylate (10 mL,9.36×10⁻² mol) were added and the suspension stirred. The flask washeated in a thermostatted oil bath at 90° C. and when the temperaturehad equilibrated ethyl-2-bromoisobutyrate (0.137 mL, 9.34×10⁻⁴ mol,[MMA]0:[In]0=100:1) was added. Samples (1-2 ml) were taken periodicallyafter initiator was added. Conversions were calculated by gravimetryheating sample to constant weight overnight at 90° C. under vacuum. Thepolymer was then diluted in THF and passed through basic aluminum oxidein order to remove the copper catalyst which has gone into solution.

TABLE Polystyrene Supported Atom Transfer Polymerisation of MMA intoluene [lig]/ Time Conv. Mnth^(c) Mn(SEC) Type Support [Cu]^(b) (min)(%) (g/mol) (g/mol) PDI ATP / 2 60 15 1 500 3 430 1.14 360 80 8 010 9050 1.11 PS-SAT PS2 1.25 33 29.6 2 960 14 020 1.55 P 83 47.2 4 720 14760 1.62 120 55.6 5 560 16 510 1.51 185 66.3 6 630 16 520 1.56 245 72.27 230 15 500 1.66 300 77.5 7 760 15 590 1.66 363 83.6 8 370 16 230 1.62PS-SAT PS4 2 35 25.6 2 600 8 125 1.47 P 310 84 8 400 11 150 1.63 PS-SATPS6 1.25 30 25.1 2 510 7 530 1.45 P 61 36.7 3 670 8 670 1.54 120 49.4 4940 10 215 1.51 180 60.1 6 010 11 140 1.53 240 68.6 6 860 11 740 1.51300 75.2 7 530 11 670 1.56 PS-SAT PS6 bis 1.25 32 25.1 2 510 6 950 1.41P 60 35.5 3 550 8 170 1.41 147 55.1 5 510 9 880 1.41 196 62.6 6 260 10590 1.41 240 67.5 6 750 10 710 1.43 300 73.5 7 360 11 370 1.42 PS-SATPS7 1 31 20.9 2 100 8 320 1.42 P 300 53.3 5 300 12 050 1.45 PS-SAT PS7 231 28.5 2 800 7 580 1.39 P 300 70 7 010 11 890 1.39 ^(b)Here [lig] isequal to the concentration of ligand functions on the polystyrenesupport. ^(c)Mn(th) = ([MMMA]0/[I]0 × MWMMA) × conversion, where MWMMAis the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is theinitial concentration ratio of MMA to initiator.

Effect of the Amount of Polystyrene Supported Ligand

TABLE Effect of the amount of polystyrene support on polystyrenesupported atom transfer polymerisations of MMA in toluene Sup- [lig]/Time Conv. Mnth^(c) Mn[SEC] port [Cu]^(b) (min) (%) (g/mol) (g/mol) PDIPS7 1  31 20.9 2090 8320 1.42  60 28.0 2800 8790 1.48 123 38.5 385010510 1.44 186 45.2 4520 11190 1.45 253 50.4 5040 12550 1.39 300 53.35330 12050 1.45 PS7 2  31 28.5 2850 7580 1.39  60 35.7 3570 8110 1.43123 50.8 5080 9970 1.39 186 59.8 5980 11130 1.36 251 63.4 6340 11070 1.4300 70.0 7010 11390 1.39 PS7 3  31 34.9 3490 7870 1.43  60 45.5 45509630 1.42 123 60.9 6090 11390 1.44 186 69.5 6950 12140 1.48 252 78.97900 12940 1.48 300 82.7 8280 13450 1.48 PS7 4  31 37.8 3780 85900 1.55 60 51.0 5100 9700 1.63 123 69.7 6970 11120 1.68 186 81.1 8120 122301.66 252 87.2 8730 13510 1.59 300 89.2 8930 13650 1.59 ^(b)Here [lig] isequal to the concentration of ligand functions on the polystyrenesupport. ^(c)Mn(th) = ([MMMA]0/[I]0 × MWMMA) × conversion, where MWMMAis the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is theinitial concentration ratio of MMA to initiator.

The (di)Amine Route

TABLE Experimental data for the PS-SATP of MMA mediated by coppercatalyst complexed by different supports synthesised following the(di)amine route time Conv. Mn Mn PDI Support name [Lig]0/[Cu]0 (min) (%)(th)^(b) (SEC) (SEC) E PS-EDA-lig ˜3 29 34.0 3 400 7 020 2.43 241 96.0 9610 13 900 2.09 G PS-TAEA-lig 2.9 36 36.6 3 660 12 375 2.06 312 95.2 9530 15 890 1.95 H PS-HEMDA-lig 2 30 25.8 2 580 16 050 1.78 180 74.7 7480 16 250 1.77 292 93.5 9 360 16 150 1.8 F1 PS-DETA-lig ˜5 36 44.1 4410 10 440 2.61 67 62.3 6 230 11 570 2.31 131 83.1 8 320 12 950 2.15 18892.7 9 280 14 120 2.08 250 99.1 9 920 17 110 1.79 F2 PS-DETA-lig ˜5 2938.6 3 860 9 200 2.02 62 62.0 6 200 11 080 1.92 126 82.2 8 230 13 2501.86 181 90.9 9 100 14 340 1.86 241 96.6 9 670 14 640 1.89 ^(b)Mn(th) =([MMMA]0/[I]0 × MWMMA) × conversion, where MWMMA is the molecular weightof methyl methacrylate and [MMMA]0/[I]0 is the initial concentrationratio of MMA to initiator.

The Amino-hexanol Route

TABLE Experimental data for the PS-SATP of MMA mediated by coppercatalyst complexed by different supports synthesized following theamino-hexanol route time Conv. Mn PDI Support name [Lig]0/[Cu]0 (min)(%) Mn(th)^(b) (SEC) (SEC) PS7 PS-lig 2 31 28.5 2 850 7 580 1.39 60 35.73 570 8 110 1.43 123 50.8 5 080 9 970 1.39 186 59.8 5 980 11 130 1.36251 63.4 6 340 11 070 1.4 300 70.0 7 010 11 890 1.39 K1 PS-AHO-lig 2 3027.1 2 710 13 880 1.81 64 42.4 4 240 14 540 1.78 119 58.9 5 890 15 6701.75 180 70.6 7 070 15 870 1.76 244 79.8 7 990 18 040 1.6 292 85.6 8 57018 250 1.63 K2 PS-AHO-lig 2 30 26.8 2 680 10 370 1.6 64 44.0 4 400 12660 1.53 119 61.0 6 100 14 730 1.53 180 72.9 7 300 16 230 1.48 244 82.58 260 16 660 1.51 292 87.4 8 750 18 080 1.46 L PS-AHO-lig 2 30 12.9 1290 26 130 1.8 64 19.1 1 910 26 950 1.81 119 27.3 2 730 29 210 1.79 18033.9 3 390 29 390 1.83 244 38.1 3 810 30 750 1.78 292 42.9 4 290 29 9201.84 ^(b)Mn(th) = ([MMMA]0/[I]0 × MWMMA) × conversion, where MWMMA isthe molecular weight of methyl methacrylate and [MMMA]0/[I]0 is theinitial concentration ratio of MMA to initiator.

Reinitiation Experiments

In a typical reinitiation experiment, CuBr (0.134 g, 9.34×10⁻⁴ mol) andthe macroinitiator (x grams, depending on the experimental molecularweight obtained from SEC and assuming that PDI=1,[macroinitiator]:[Cu]=0.182:1) were placed in a predried Schlenk flaskwhich was evacuated and then flushed with nitrogen three times.Deoxygenated toluene (30 ml, 75% v/v) and deoxygenated methylmethacrylate (10 mL, 9.36×10⁻² mol, [MMA]0:[Cu]0=900:1) or deoxygenatedbenzyl methacrylate (10 ml, 5.92×10⁻² mol, [BzMA]0:[Cu]0=63.22:1) wereadded and the suspension stirred until all the macroinitiator isdissolved. The flask is then submitted to three Freeze-Pump-Thaw cycles(FPT). When the temperature had equilibrated to room temperature,N-^(n)pentyl-2-pyridine methanimine ligand (1) (0.36 ml, 1.87×10⁻³ mol[Lig]0:[Cu]0=2:1) is added by syringe and the flask is heatedstraightforward in a thermostatted oil bath at 90° C. Samples (1-2 ml)were taken periodically using syringes after the start of the heating.Conversions were calculated by gravimetry heating sample to constantweight overnight at 90° C. under vacuum. The polymer was then diluted inTHF and passed through basic aluminum oxide in order to remove thecopper catalyst which has gone into solution.

TABLE molar ratios of components used in reinitiation experiments*** Ex-Monomer pentyl peri- Macro- 2 ligand ment initiator^(a) [In] [MMA] [Lig][CuBr] 1 PMMA(A) 0.182 100 2 1 2 PMMA(S) 0.182 100 2 1 3 PMMA(P) 0.182100 2 1 4 PMMA(L) 0.182 100 2 1 ^(a)PMMA (A) synthesised followingconditions [MMA]:[CuBr]:[lig]:[E2BI] = 100:1:2:1 PMMA (S) synthesisedfollowing conditions [MMA]:[CuBr]:[Si-lig S4 ]:[E2BI] = 100:1:1:1 PMMA(P) synthesised following conditions [MMA]:[CuBr]:[PS-lig PS6 ]:[E2BI] =100:1:1:1

PMMA (L) synthesised following conditions [MMA]:[CuBr]:[Si-ligS4]:[E2BI]=100:1:2:1

These results are shown in FIG. 5.

TABLE Data for macrointiation experiments using different monomersExperi- Macro- Time Conv % Mnth Mnexp ment init. (min) 2^(nd) pol °(g/mol) PDI 1 PMMA (A) 0 0  7616 1.19  34 10.5 13374 12546 1.17  63 15.115898 14760 1.21 130 22.1 19749 19230 1.25 61%-3 h 186 26.9 22419 222701.3 244 30.6 24419 25210 1.31 278 32.5 25507 27570 1.29 2 PMMA (S) 0 016575 1.46 33 10.4 22293 17130 1.28 62 15.1 24873 22510 1.39 129 22.228761 29540 1.25 2 h 185 26.7 31244 31330 1.27 241 30.5 33366 34640 1.25278 32.7 34534 35810 1.25 3 PMMA (P) 0 0 13105 1.5 33 12.1 19773 187701.17 62 17.1 22493 20510 1.19 129 23.2 25853 23940 1.20 185 28.2 2860826300 1.20 241 31.8 30617 28440 1.21 278 32.8 31143 29150 1.22 4 PMMA(L) 0 0  6896 1.46 33 10.9 12862 12250 1.19 62 15.7 15508 14340 1.19 12923.2 19704 18250 1.18 185 27.3 21901 20480 1.19 69% 2h 241 30.8 2381216130 1.19 278 33.3 25198 24320 1.19

Block Copolymerisation

TABLE Molar ratios of components used in reinitiation experiments Ex-pentyl peri- Macro- Monomer 2 ligand ment initiator^(a) [In] [MMA] [Lig][CuBr] 5 PMMA (A) 0.182 63.22 2 1 6 PMMA (S) 0.182 63.22 2 1 7 PMMA (P)0.182 63.22 2 1 8 PMMA (L) 0.182 63.22 2 1 ^(a)PMMA (A) synthesisedfollowing conditions [MMA]:[CuBr]:[lig]:[E2BI] = 100:1:2:1 PMMA (S)synthesised following conditions [MMA]:[CuBr]:[Si-lig S4]:[E2BI] =100:1:1:1 PMMA (P) synthesised following conditions [MMA]:[CuBr]:[PS-ligPS6]:[E2BI] = 100:1:1:1 PMMA (L) synthesised following conditions[MMA]:[CuBr]:[Si-lig S4]:[E2BI] = 100:1:2:1

TABLE Data for macrointiation experiments using different monomersExperi- Macro- Time Conv % Mnth Mnexp ment init. (min) 2^(nd) pol °(g/mol) PDI 1 PMMA (A) 0 0  7616 1.19 38 18.4 18890 17536 1.59 64 23.021670 19861 1.28 131 34.6 28790 26391 1.34 61%-3 h 261 73.0 52308 510281.83 309 79.6 56348 45112 1.99 358 80.2 56680 42580 2.00 6 PMMA (S) 0 021828 1.47 2 33 19.9 33985 29395 1.75 59 22.6 35647 30172 1.62 126 35.443482 35658 1.58 3 h 62% 256 59.6 58283 45600 1.83 304 71.1 65325 546981.80 353 75.8 68207 55380 1.79 7 PMMA (P) 0 0 14676 1.23 35 19.6 2668924023 1.42 3 h 66 29.1 32497 28194 1.51 52% 127 42.7 40790 35295 1.73257 63.3 53397 44560 1.71 305 77.7 62208 53841 1.63 354 83.8 65984 431051.81 8 PMMA (L) 0 0  6896 1.46 36 16.7 17097 61 22.5 20673 128 37.029552 258 49.1 36922 69% 2 h 306 52.2 38444 355 60.7 44070 28240 1.83

Recyclability

TABLE Recycling experiments carried out with support PS7 for thepolymerisation of MMA by polystyrene supported atom transferpolymerisation; [MMA]:[Cu]:[PS-lig PS7]:[E2BI] = 100:1:2:1 Ex- Conver-peri- Time sion Mnth Mn(SEC) ment (min) (%) (g/mol) (g/mol) PDI First 31 28.5 2850 7580 1.39 polym.  60 35.7 3570 8110 1.43 123 50.8 5080−9970 1.39 136 59.8 5980 11130 1.36 231 63.4 6340 11070 1.4 300 70.07010 11890 1.39 Recycling 1  29 4.06 400  69 7.04 700 134 15.4 154012000 1.68 172 22.5 2250 13810 1.61 255 38.1 3810 14760 1.65 329 52.15210 16560 1.61 365 58.5 5850 16880 1.59 Recycling 2  76 1.90 190 1254.45 445 176 8.00 801 265 17.1 1714 336 25.7 2575

What is claimed is:
 1. A catalyst for the addition polymerization ofolefinically unsaturated monomers comprising a supported ligand ofGeneral Formula 1: S(D)_(n)  Formula 1 where: S is the support, D is acompound attached to the support, said compound being capable ofcomplexing with a transition metal ion, and n is an integer of one ormore; in combination with a) a compound of: MY  Formula 30 where: M is atransition metal in a low valency state or a transition metal in a lowvalency state co-ordinated to at least one co-ordinating non-chargedligand, wherein the transition metal is selected from the groupconsisting of Cu(I), Fe(II), Co(II), Ru(II), Ni(II), Rh(I), and Ru(III),and Y is a mono- or polyvalent counter ion; and b) an initiator compoundcomprising a homolytically cleavable bond with a halogen atom.
 2. Acatalyst for use in the polymerisation of olefinically unsaturatedmonomers, comprising a compound of general formula: ((SD)_(c)M)^(d+)A  Formula 52 where: M=a transition metal in a low valency state or atransition metal co-ordinated to at least one co-ordinating non-chargedligand, wherein the transition metal is selected from the groupconsisting of Cu(I), Fe(II), Co(II), Ru(II), Ni(II), Rh(I), and Ru(III),S=a support, D=a compound attached to the support, the compound beingcapable of complexing with a transition metal, d=an integer of 1 or 2,c=an integer of 1 or 2, and A=a monovalent or divalent counter ion andan initiator compound having a homolytically cleavable bond with ahalogen atom.
 3. A catalyst according to claim 2, wherein theco-ordinating ligand is (CH₃CN)₄.
 4. A catalyst according to claim 1,wherein the initiator compound is selected from the group consisting of:

where: R is independently selectable and is selected from straight,branched or cyclic alkyl, hydrogen, substituted alkyl, hydroxyalkyl,carboxyalkyl or substituted benzyl, X is a halide.
 5. A catalystaccording to claim 1, wherein compound D is a diimine.
 6. A catalystaccording to claim 5, wherein one of the nitrogens of the diimine is notpart of an aromatic ring.
 7. A catalyst according to claim 5, whereinthe diimine is selected from the group consisting of: a1,4-diaza-1,3-butadiene

where R₁, R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be varied independently and R₁,R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be H, straight chain, branched chain orcyclic saturated alkyl, hydroxyalkyl, carboxyalkyl, aryl, CH₂Ar (whereAr=aryl or substituted aryl) or a halogen; and R₃ to R₉ mayindependently be selected from the group described for R₁, R₂, R₁₀, R₁₁,R₁₂ and R₁₃ or additionally OC_(n)H_(2n)+₁, (where n is an integer from1 to 20), NO₂, CN or O═CR (where R=alkyl, benzyl PhCH₂ or a substitutedbenzyl).
 8. The catalyst according to claim 5, wherein D exhibits achiral centre α to one of the nitrogen groups.
 9. The catalyst accordingto claim 7, wherein D is a compound of general Formula 3 which comprisesone or more fused rings on the pyridine group.
 10. The catalystaccording to claim 7, wherein one or more adjacent R₁, and R₃, R₃ andR₄, R₄ and R₂, R₁₀ and R₉, R₈ and R₉, R₈ and R₇, R₇ and R₆, R₆ and R₅groups are selected from the group consisting of C₅ to C8 cycloalkyl,cycloalkenyl, polycycloalkyl, polycycloalkenyl and cyclicaryl.
 11. Thecatalyst according to claim 7, wherein the diimine compound iscovalently attached to the support via positions R1, R2, R9, R10, R11,R12 or R13.
 12. A process for the production of, a catalyst according toclaim 5, comprising the steps of: a) providing a functionalised support;b) providing a ligand precursor, wherein one of the functionalisedsupport or the ligand precursor comprises a primary amine, and the otherof the functionalised support or the ligand precursor comprises analdehyde or ketone group; and c) reacting the primary amine with thealdehyde or ketone to form a diimine compound covalently attached to thesupport.
 13. Process according to claim 12, wherein the diimine compoundproduced is then mixed with a transition metal halide to produce adiimine co-ordinated to a transition metal.
 14. Process according toclaim 13, wherein the transition metal halide is CuCl or CuBr.
 15. Aprocess for the addition polymerisation of one or more olefinicallyunsaturated monomers comprising the use of a catalyst according toclaim
 1. 16. A process according to claim 15, wherein the olefinicallyunsaturated monomer is selected from a methacrylate, an acrylate, astyrene, a methacrylonitrile or a diene.
 17. A process according toclaim 14, wherein the catalyst is used at a temperature between −20° C.and 200° C.
 18. A process according to claim 15, additionally comprisingthe use of a free-radical inhibitor.
 19. A process according to claim15, wherein the amount of D: MY is between 0.01 to 1000 and ratio of MY:initiator is 0:0001 to
 1000. 20. The catalyst according to claim 4,wherein X is selected from the group consisting of I, Br, F and Cl. 21.The catalyst according to claim 7, wherein R₁, R₂, R₁₀, R₁₁, R₁₂, andR₁₃ is a phenyl, or substituted phenyl, wherein the substitution of thephenyl is as described for R₃ to R₉.
 22. The catalyst according to claim10, wherein the the C₅ to C₈ cycloalkyl, cycloalkenyl, polycycloalkyl,polycycloalkenyl or cyclic aryl group is a cyclohexyl, cyclohexenyl ornorborneyl.